Novel Flux Enhancing Agent for Improving Composite Polyamide Reverse Osmosis Membrane Performance

ABSTRACT

The present disclosure describes an additive that may be used in the manufacture of thin-film polyamide composite membranes. Thin-film polyamide composite membranes are used in filtration processes, such as reverse osmosis and nanofiltration. The additive may be an amino-siloxane compound. The amino-siloxane compound includes repeated groups of silicon bonded to oxygen with at least one amine functional group. Optionally, the amino-siloxane compound may also include a hydrophilic group. The additive reacts with an aqueous phase and an organic phase to form a thin polyamide film on a porous substrate.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional application of U.S. application Ser. No.13/590,867, filed Aug. 21, 2012, which is hereby incorporated byreference.

FIELD

The present disclosure relates generally to filtration membranes andmore particularly to reverse osmosis and nanofiltration membranes.

BACKGROUND

Semi-permeable membranes are used for extracting a solvent, for examplewater, from a solution or mixture and rejecting unwanted solutes orsolids, such as salts and other contaminants. The semi-permeablemembranes may be cross-linked polyamide composite membranes thatcomprise a separation layer supported upon a porous substrate. Theseparation layers are thin to maximize membrane performance while theporous substrate provides the necessary structural support. Theseparation layer may be a thin-film polyamide layer that is formed,coated or deposited on a porous polysulfone support. The membrane may beused in reverse osmosis or nanofiltration processes.

The separation layer may be formed on the porous support by varioustechniques, including interfacial polymerization. Interfacialpolymerization forms a thin-film polyamide at an interface between anaqueous solution and a water immiscible organic solvent. The interfaceis positioned at or near the surface of the porous substrate tofacilitate depositing the thin-film on the substrate.

Isopropyl alcohol can be added to the aqueous solution duringinterfacial polymerization. The isopropyl alcohol improves permeabilitycharacteristics but at the expense of solute rejection characteristics.Additionally, significant amounts of isopropyl alcohol are required toachieve the permeability improvements, which may increase health andsafety risks that are associated with the volatility of isopropylalcohol.

SUMMARY

This specification describes a chemical additive that is useful informing thin-film polyamide composite membranes.

This specification also describes thin-film polyamide compositemembranes comprising a substrate, and a coating layer that is made fromreactants comprising an aqueous phase, an organic phase and theadditive.

This specification also describes methods of making thin-film polyamidecomposite membranes. The methods comprising reacting an aqueous phase,an organic phase and an additive. The reaction occurs at or near thesurface of the substrate and results in a polyamide separation layerforming on the substrate.

The aqueous phase may include amine monomers, polyamine monomers orother amines. The organic phase may include polyacyl halide monomers.The substrate may be a porous substrate.

The additive may be an amino-siloxane compound. An amino-siloxanecompound includes repeated groups of silicon bonded to oxygen with atleast one amine functional group. Optionally, the additive may includeanother functional group that increases the hydrophilicity of theadditive, for example an oxygen and alkyl or aryl containing group, suchas an ether group, polyether group or the like. The additive may causecovalent bonding of the compound with portions of a reaction product ofthe aqueous and organic phases.

Without being bound by theory, the additive may reduce the surfacetension of the aqueous phase. The reduced surface tension may increasethe rate at which amines within the aqueous phase cross theaqueous-organic interface into the organic phase. In contrast to otherknown chemical additives, such as alcohols, amides, sulfoxides andketones, the additive of the present specification may also participatein the interfacial polymerization reaction. This participation maycreate silicon-containing materials that are incorporated into thepolyamide matrix. The additive may also favourably affect cross-linkingwithin the interfacial amide polymer.

The resulting membrane is useful, for example, in reverse osmosis ornanofiltration.

Additionally, the residual amino groups of the additive may change thethin-film polyamide composite membrane's zeta potential. Thin-filmpolyamide composite membranes with zeta potentials close to zero, whichis reflective of a more neutral surface charge, may have a higher theresistance to fouling.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation of Fourier Transformed Infra-redspectroscopy data from example thin-film polyamide composite membranes;

FIGS. 2A through 2D are a series of scanning electron microscope resultsobtained from example thin-film polyamide composite membranes;

FIGS. 3A and 3B are graphic representations of passage data, over time,from example thin-film polyamide composite membranes;

FIGS. 4A and 4B are graphic representations of permeability data andrejection data, respectively, from example thin-film polyamide compositemembranes;

FIG. 5 is a graphical representation of zeta potential data over a pHrange from example thin-film polyamide composite membranes;

FIGS. 6A and 6B are graphic representations of the permeability data andthe solute rejection data, respectively, from example thin-filmpolyamide composite membranes; and

FIG. 7 is a photograph of an amino-siloxane compound with an acyl halidein an organic solution.

DETAILED DESCRIPTION

A thin-film polyamide composite membrane may comprise a substrate, acoating layer, wherein the coating layer is made from an aqueous phase,an organic phase and an additive. These thin-film polyamide compositemembranes have suitable permeability characteristics to extract, forexample via reverse osmosis or nanofiltration, potable water frombrackish water or seawater.

The substrate provides the structural support for the coating layer. Thesubstrate may be a porous substrate selected from a number of materialsthat have pore sizes that are large enough to permit the passage ofwater, or other permeates, therethrough. Examples of suitable poroussubstrate materials include fibrous and nanofibrous webs, sinteredmetals and sintered ceramics. Additionally, polymers such aspolysulfones, polycarbonates, polyolefins, polyamides, polyimides,polynitriles, polyimines, polyphenylene ethers, polyketones,polyetherketones, halogenated polymers including polyvinylidine fluorideand the like can be used to make a suitable porous substrate.

The coating layer may comprise a polymer such as a polyamide film thatis thin to optimize the filtration performance of the membrane.Performance of the membrane may be characterized by the solventpermeability properties and the solute passage properties of themembrane. Constituents of the aqueous phase, organic phase and theadditive participate in the formation of the polyamide film.

The aqueous phase can include monomeric primary polyfunctional amines ormonomeric secondary polyfunctional amines. The monomeric polyfunctionalamines may include cyclic polyfunctional amines, for example piperazine;acyclic polyfunctional amines such as 1,2-ethanediamaine; substitutedcyclic polyfunctional amines, for example methyl piperazine and dimethylpiperazine; aromatic polyfunctional amines, for examplemeta-phenylenediamine, o-phenylenediamine and p-phenylenedamine;substituted aromatic polyfunctional amines, for examplechlorophenylenediamine, N,N¹-dimethyl-1,3-phenylenediamine;multi-aromatic ring polyfunctional amines, for example benzidine;substituted multi-aromatic ring polyfunctional amines such as3,3¹-dimethylbenzidene, 3,3¹-dichlorobenzidine; or mixtures thereof. Theaqueous phase can include other constituent compounds, for exampletriethylammonium camphorsulfonate.

The organic phase can include aromatic polyacyl halides, for example di-or tri-carboxylic acid halides such as trimesoyl chloride (1,3,5-benzenetricarboxylic acid chloride), isophthaloyl chloride, terephthaloylchloride, 1,3,5-cyclohexanetricarbonyl chloride,1,2,3,4-cyclopentanetetracarbonyl chloride, trimesoyl bromide(1,3,5-benzene tricarboxylic acid bromide), isophthaloyl bromide,terephthaloyl bromide, trimesoyl iodine (1,3,5-benzene tricarboxylicacid iodide), isophthaloyl iodide, terephthaloyl iodide and mixtures ofdi-tri and tri-tricarboxylic acid halides such as trimesoyl halide andthe isomeric phthaloyl halides. The aromatic polyacyl halides may bereplaced by, or mixed with, aromatic di or tri sulfonyl halides,aromatic di or tri isocyanates, aromatic di or tri chloroformates, oraromatic rings substituted with mixtures of the above. The polyacylhalides may also be substituted to improve protection from environmentalattack. The organic solvent is immiscible with water and may beimmiscible or sparingly miscible with polyhydric compounds and mayfurther comprise paraffins such as n-pentane, n-hexane, n-heptane,cyclopentane, cyclohexane, methylcyclopentane, naphtha, mixtures ofaliphatic hydrocarbons sold under the name Isopar®, mixtures ofaliphatic and aromatic hydrocarbons; or halogenated hydrocarbons such asthe Freon® series of halogenated solvents.

The additive may be an amino-siloxane compound with repeated groups ofsilicon bonded to oxygen with at least one amine functional group.Optionally, the additive may include a hydrophilic functional group thatincreases the hydrophilicity of the additive. For example, the optionalhydrophilic functional group may be an oxygen and alkyl- oraryl-containing group, such as an ether, polyether or the like.

An example amino-siloxane compound is OFX-8600, which is commerciallyavailable from Dow Corning® Singapore Pte. Ltd. OFX-8600 contains anamino-siloxane component of the following formula (1) (CAS RegistryNumber 237753-63-8):

wherein R is CH₃ to C₁₅H₃₁; X is 75% of —CH₂CH(OH)CH₂OH and 25% H; and nis an integer between 1 and 100. (1)

Another example of an amino-siloxane compound is a compound synthesizedby the reactions of formulas (2) and (3):

The reaction product shown by formula (3) is referred to as siloxane-1.U.S. Pat. No. 4,757,121 to Tanaka et al. describes silicone-basedsoftening agents for fibers that are formed by similar chemistry asformulas (2) and (3), the disclosure of which is incorporated herein byreference. The term “−Pressure” in formula (3) refers to a vacuum todraw off low-boiling constituents.

The experimental examples provided below demonstrate that thin-filmpolyamide composite membranes, which include either of the additivesOFX-8600 or siloxane-1, function as semi-permeable membranes useful forreverse osmosis. Based upon these experimental results, the inventorsexpect that amino-siloxane compounds that contain amino side-groups and,optionally hydrophilic side groups, will similarly function as usefuladditives in thin-film polyamide composite membranes for reverse osmosisand nanofiltration.

The chemical structures provided herein are some examples ofamino-siloxane compounds that are expected to be useful as an additive.

An example class of amino-siloxane compounds useful as an additive isrepresented by the following formula (4):

where R1 and R2 may be the same or different, and are C1-C20 alkyl oralkoxy groups; R3 may be a C1-C4 alkyl group, or H; Q is either —(CH₂)₃—or —CH₂CH(CH₃)CH₂—; X is either —CH₂CH(OH)CH₂OH or H; a, b, c, d, e areintegers such that the sum of a+b+c+d+e<100, if b is 0, then d or e mustbe greater than 0, if d is 0, then b or e must be greater than 0; and ife is 0, then b or d must be greater than 0; and, y1, y2, z, z2 are eachintegers between 0 and 10. (4)

Another example class of amino-siloxane compounds useful as an additiveis represented by the following formula (5):

wherein a and b are integers between 1 and 100 and the sum of a+b is notgreater than 100. (5)

Another example class of suitable amino-siloxane compounds useful as anadditive may be represented by the following formula (6):

wherein a, b and c are integers between 1 and 100, the sum of a+b+c isnot greater than 100 and x is an integer between 1 and 50. (6)

Another example class of suitable amino-siloxane compounds useful as anadditive may be represented by any of the following compounds:

Thin-film polyamide composite membranes are made by reacting the aqueousphase, the organic phase and the additive on or near the surface of thesubstrate. Optionally, the additive is added to the aqueous phase. Inthis option the aqueous phase, inclusive of the additive, is a singlecomponent that reacts with the organic phase in a two-component reactionprocess.

Processes for making the thin-film polyamide composite membranes areknown to those skilled in the art. One example of a useful process isinterfacial polymerization. Interfacial polymerization includescontacting the aqueous phase with the substrate. The organic phase isadded to and reacts with the aqueous phase. The aqueous phase and theorganic phase are immiscible and, therefore, when they come into contactan interface is formed. The interface is located at or near the surfaceof the substrate. At the interface, the amine monomers in the aqueousphase react with the polyacyl halide monomers in the organic phase toform an amide polymer that is deposited on or near the surface of thesubstrate. The rate of polymerization, and hence the rate of forming thethin-film, may be modified by temperature or the addition of catalysts.The interfacial polymerization reaction may be carried out at atemperature ranging from about 5° C. to about 60° C., preferably fromabout 10° C. to about 40° C. Optionally, the additive can be added tothe aqueous phase before the organic phase is added.

The reaction of the aqueous phase, the organic phase and the additivemay occur by batch-methods which employ, for example, a hand-frameapparatus suitable for laboratory scale preparations, as describedbelow. The reaction of the aqueous phase, the organic phase and theadditive may also occur by continuous processes, such as roll-to-rollmethods for pilot scale and full-scale production.

The hand frame coating apparatus consists of a matched pair of framesfor holding the substrate for coating. A porous substrate is soaked inde-ionized water for at least 30 minutes and then fixed between two 8inch by 11 inch (approximately 20.3 cm by 27.9 cm) plastic frames andkept covered with water until use. Excess water is removed from theporous substrate and then one surface of the porous substrate is coatedwith the aqueous phase. In one option, the additive can be added to theaqueous phase prior to coating the porous substrate. In another option,the additive can be added to the porous substrate separately from theaqueous process.

The upper portion of the frame confines the aqueous phase to the surfaceof the porous substrate. After a period of time, for example 120seconds, the aqueous phase may be removed from the surface of the poroussubstrate by tilting the frame to pour off the aqueous phase until onlyisolated drops of the aqueous phase, optionally inclusive with theadditive, are visible on the coated surface of the porous substrate. Thecoated surface of the porous substrate may be treated with a gentlestream of air to remove the isolated drops of the aqueous phase. Someamount of the aqueous phase remains within or upon the surface of theporous substrate as an aqueous coating. The aqueous coated surface ofthe porous substrate is then contacted with the organic phase and theconstituents of the aqueous phase, the organic phase and the additivereact.

The reaction product of the aqueous phase, the organic phase and theadditive can be deposited upon or near the surface of the poroussubstrate. For example the reaction product can be a thin-filmpolyamide. The reaction product may also include a compound that is thereaction product of the organic phase and the additive.

Experimental Examples of Additive Synthesis

The inventors synthesized an example amino-siloxane compound by thereactions of formulas (2) and (3) from above to form siloxane-1. A 100mL 3-neck round bottom flask equipped with a thermometer and stirrer wasused to react 2.06 g of 3-(N-2-aminoethyl)amino propyl methyl dimethoxysilane; 25.5 g of octamethyl cyclotetrasiloxane; 0.81 g of hexamethyldisiloxane; 0.022 g of potassium hydroxide and 0.142 g of dimethylsulfoxide. The reaction proceeded for six hours at 110° C., under astream of nitrogen gas. Next 0.024 g of acetic acid was added and themixture was further agitated at 100° C. for an hour. The reactionmixture was then stripped of low-boiling constituents at 100° C. for twohours, under vacuum. This produced the reaction product of formula (2)above.

A 10 g measure of the reaction product of formula (2) was added to a 100mL round-bottom flask with 5 g of toluene and 0.6475 g of glycidylalcohol and the mixture was stirred for five hours at 80° C. Thismixture was then stripped, under vacuum, of low-boiling constituents at100° C. for two hours, to produce siloxane-1 the product of formula (3)above.

FIG. 1 depicts the Fourier Transformed Infra-red spectral comparison ofOFX-8600 (dotted line) and siloxane-1 (shown in the solid line). Thespectra are approximately 95% similar with differences in functionalgroups, at least around the frequency of about 3000 cm⁻¹. Thesedifferences may be explained by a minor component of aliphatic alcoholspresent in the OFX-8600.

Experimental Examples of Membranes

The following description of example thin-film polyamide compositemembranes includes chemical structures, formulas, masses and ratios thatare provided as examples and not as limitations.

The example thin-film polyamide composite membranes were made and testedusing standard laboratory procedures that reflect larger-scaleindustrial processes, tests and applications.

The following example thin-film polyamide composite membranes were allformed on a porous polysulfone substrate using the hand frame apparatustechnique described above. Semi-permeable membranes with similarproperties may be formed by various techniques, for example roll-to-rollcoating and other processes that are used in larger-scale, industrialprocesses for manufacturing thin-film polyamide composite membranes.

Example 1 was formed using the following compounds:meta-phenylenediamine (MPD), triethylammonium camphorsulfonate (TEACSA),and trimesoyl chloride (TMC) in a mass ratio of 1.5:8:0.2, respectively.To achieve these ratios, 1.5 g of MPD and 8 g of TEACSA were mixed withenough water to make a total mass of 100 g of the aqueous phase. Theorganic phase was made by combining 0.2 g of TMC with 99.8 g of Isopar®G for a total mass of 100 g. No additive was included in Example 1,which is provided as a comparator for Example 2 as described below.

To investigate the addition of an amino-siloxane additive on the surfacecharacteristics of a thin-film polyamide composite membrane Example 2was formed using the same compounds, in the same mass ratio, asExample 1. Example 2 included OFX-8600 as the amino-siloxane additive ata concentration of 250 ppm, in relation to the total mass of the aqueousphase. To achieve the 250 ppm concentration of OFX-8600, the aqueousphase was made with 1.5 g of MPD, 8 g of TEACSA, 0.025 g of OFX-8600 andenough water was added to make an aqueous phase with a final mass of 100g. The organic phase was made as described in Example 1.

Example 3 was formed using the following compounds: MPD, TEACSA and TMCin a mass ratio of 2.75:6.6:0.2, respectively. The aqueous phase wasmade with 2.75 g of MPD, 6.6 g of TEACSA and enough water to make anaqueous phase with a final mass of 100 g. The organic phase was made bycombining 0.2 g of TMC with 99.8 g of Isopar® G for a total mass of 100g. Example 3 does not contain any amino-siloxane additive and it isprovided as a comparator for Examples 4 to 7.

Examples 4 to 7 were formed using the same compounds as Example 3 andthese examples included various concentrations of OFX-8600 as theamino-siloxane additive, as set out in Table 1 below. To achieve theseconcentrations of OFX-8600 in the aqueous phase, 2.75 g of MPD, 6.6 g ofTEACSA and one of 0.1 g, 0.025 g, 0.05 g or 0.08 g of OFX-8600 (Examples4, 5, 6, and 7 respectively) were mixed with enough water to make atotal aqueous-phase mass of 100 g. The organic phase was made asdescribed above for Example 3.

TABLE 1 Amount of OFX-8600 in Experimental Examples 3 to 7. OFX-8600Example (ppm in relation to total mass of aqueous phase) 3 0 4 1000 5250 6 500 7 800

FIGS. 2A through 2D are scanning electron microscope images of thesurface of the thin-film polyamide composite membranes of Examples 1 to4, respectively. The scale bar presented in each image is 1 micron. Atthis scale Example 2, which included the OFX-8600, did not exhibit anyvisually apparent difference as compared to Example 1, which lackedOFX-8600. However, in Example 4, which included 1000 ppm of OFX-8600, achange in membrane morphology is visible, which may have resulted in anincrease in the active area of the separation layer (see FIG. 2D).

As described in Table 1 above, Example 5 includes the OFX-8600 materialadded at a concentration of 250 ppm, in relation to the total mass ofthe aqueous phase.

The permeability and passage characteristics of Examples 3, 4 and 5 weretested in a reverse osmosis cell by 15 minutes of flushing with a 2000ppm saline solution at a pressure of 225 psi (approximately 15.5 bar).These conditions are typical for brackish water reverse osmosisprocesses. Table 2 provides the permeability (A) and passage (P) resultsof samples taken over a ten minute collection period. The A valuerepresents the permeability and can be calculated by formula (7):

A=permeate volume/(membrane area×time×net driving pressure).   (7)

Permeate volume is reflected by the units of 10⁻⁵ cm³. Membrane area ismeasured in cm², time is measured in seconds and the net drivingpressure is measured in atms at 25° C. The net driving pressure is theaverage trans-membrane pressure less the osmotic pressure differencebetween the saline solution and the permeate.

The P values are determined by the solute concentration in the permeatedivided by the average solute concentration in the saline solution andin the concentrate, expressed as a percentage by the following formula(8):

Passage (%)=permeate concentration/((feed concentration+concentrateconcentration)/2).   (8)

TABLE 2 Permeability (A) and passage (P) results for Examples 3, 4 and5. Mean Mean Permeability Passage (A) (P) Example 3 6.1 0.54 Example 49.68 0.55 Example 5 10.63 0.49

Table 3 below provides the mean permeability (A) results for another setof Examples 3, 4, and 5 that were tested under similar reverse osmosisconditions as described above but over a 5.5 hour time frame.

TABLE 3 Permeability (A) results for Examples 3, 4 and 5, over time.Mean Mean Percent Decrease Permeability Permeability in PermeabilitySample (A) at 0.25 h (A) at 5.5 h (A) Example 3 6.06 5.20 14.19 Example4 10.47 8.92 14.80 Example 5 9.85 8.53 13.40

The passage characteristics of Examples 3, 4 and 5 over the 5.5 hourstime frame are shown in FIG. 3A.

To investigate any concentration effect of the amino-siloxane additive,Examples 6 and 7 were made with the same, in the same mass ratios, asExample 3. As described above in Table 1, Example 6 included 500 ppm ofOFX-8600 and Example 7 included 800 ppm of OFX-8600, in relation to thetotal mass of the aqueous phase.

To test the permeability and passage functions of the example thin-filmpolyamide composite membranes, Examples 3, 4, 5, 6, 7 were placed in areverse osmosis chamber and flushed for 15 minutes by a 2000 ppm salinesolution at a pressure of 225 psi (approximately 15.5 bar), with samplescollected over 10 minutes. An additional formulation of Example 3 with10% isopropyl alcohol, on a mass basis, was also included (shown as 10%IPA in FIGS. 4A and 4B).

FIG. 4A depicts the permeability (A) of Example 4 as greater thanExample 3 and the 10% IPA formulation. Examples 5, 6 and 7 demonstratedgreater permeability than Example 4. FIG. 4B depicts the passageproperties of these examples.

FIG. 5 is a line graph that depicts the zeta potential versus pHmeasured on Examples 3 and 5 after the 5.5 hours of reverse osmosisflushing. Example 5 demonstrated an approximately 5 mV shift towards azeta potential of zero. This may reflect a lower fouling potential as aresult of utilization of the amino-siloxane additive.

To further investigate any effect of time on permeability and passageproperties, Example 8 was formed using the following compounds: MPD,TEACSA and TMC in a ratio of 4:6:0.2, respectively. To make the aqueousphase 4 g of MPD and 6 g of TEACSA were added to enough water to make afinal mass of 100 g of the aqueous phase. No additive was included inExample 8, which is provided as a comparator for Examples 9 and 10below. The organic phase was made as described in Example 3.

Examples 9 and 10 were formed using the same compounds, in the same massratio, as Example 8. Example 9 included 1000 ppm of OFX-8600, inrelation to the total mass of the aqueous phase, and Example 10 included250 ppm of OFX-8600, in relation to the total mass of the aqueous phase.To achieve these concentrations, 4 g of MPD, 6 g of TEACSA and either0.1 g (Example 9) or 0.025 g (Example 10) were combined with enoughwater to make a final mass of 100 g. The organic phase was made asdescribed above.

Table 4 below provides the permeability (A) results for Examples 8, 9and 10 over time. These membranes were tested under similar conditionsas described above for Table 2, except these examples were flushed for3.5 hours with a 32000 ppm saline solution at a pressure of 800 psi(approximately 55.2 bar). These conditions are typical of seawaterreverse osmosis processes.

TABLE 4 Permeability (A) results for Examples 8, 9 and 10, over time.Mean Mean Percent Decrease Permeability Permeability in PermeabilitySample (A) at 0.4 h (A) at 3.5 h (A) Example 8 2.94 2.68 8.84 Example 93.32 2.96 10.84 Example 10 4.67 4.19 10.28

The passage characteristics of Examples 8, 9 and 10 are shown in FIG.3B.

To investigate the synthesized siloxane-1, Example 11 was formed in ahand frame apparatus using the following compounds: MPD, TEACSA and TMCin a mass ratio of 2.75:6.6:0.2, respectively, which are the samecompounds and ratios of Example 3 above. The siloxane-1 material wasadded at a concentration of 250 ppm, in relation to the total mass ofthe aqueous phase. To achieve this concentration of siloxane-1 in theaqueous phase, 2.75 g of MPD, 6.6 g of TEACSA, 0.025 g of siloxane-1were mixed with enough water to make a total aqueous-phase mass of 100g. The organic phase was made as described above for Example 3.

The permeability and passage function of Example 11 was compared withExamples 3 and 5 in a reverse osmosis chamber by 15 minutes of flushingwith a 2000 ppm saline solution at a pressure of 225 psi (approximately15.5 bar), with samples collected over 10 minutes.

FIG. 6A shows that the permeability (A) of Example 5, which included 250ppm of OFX-8600 and Example 11 are very similar and both are higher thanExample 3, which did not include any additive. Further, the passagecharacteristics of all three samples are similar (FIG. 6B).

Experimental Example of Further Reaction Product

FIG. 7 is a photograph that shows a film of reaction product (see arrowin FIG. 7) that formed at the interface between an aqueous solution of250 ppm of OFX-8600 and an organic solution of 0.2% TMC. This film isformed in the absence of MPD and TEACSA.

Table 5 below, provides x-ray fluorescence data of Examples 3, 4 and 5,which measures amounts of silicon.

TABLE 5 Percent Silicon (mean) before and after 5.5 hours of reverseosmosis flushing. Percent Silicon after Percent Silicon 5.5 hours offlushing Sample (mean) (mean) Example 3 0.00 0.00 Example 4 0.24 0.23Example 5 0.09 0.09

The detection of silicon in these membranes and the film shown in FIG. 7indicate that the amino-siloxane compounds are able to react withdifunctional or polyfunctional acyl halides to form a reaction productthat may be incorporated within the polyamide matrix. This reactionproduct may be in addition to the polyamide film formed on the poroussubstrate by the reaction of the aqueous phase, the organic phase andthe additive.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to practice the invention, including making and using any devices orsystems and performing any incorporated methods. The patentable scope ofthe invention is defined by the claims, and may include other examplesthat occur to those skilled in the art.

What is claimed is:
 1. A composite membrane for reverse osmosis ornanofiltration, the membrane comprising: a porous substrate; a polymerlayer on a surface of the porous substrate, wherein the polymer layercomprises a reaction product of an organic phase, an aqueous phase andan amino-siloxane compound, wherein the organic phase comprises polyacylhalides and the aqueous phase comprising amines.
 2. A compound formed byreacting an organic phase and an additive, the organic phase comprisinga polyacyl halide and the additive is a compound of the formula:

wherein R1 and R2 may be the same or different, and are C1-C20 alkyl oralkoxy groups; R3 may be a C1-C4 alkyl group, or H; Q is either —(CH₂)³—or —CH₂CH(CH₃)CH₂—; X is either —CH₂CH(OH)CH₂OH or H; a, b, c, d, e areintegers such that the sum of a+b+c+d+e is less than 100, if b is 0,then d or e must be greater than 0, if d is 0, then b or e must begreater than 0; and if e is 0, then b or d must be greater than 0; and,y1, y2, z1, z2 are each integers between 0 to
 10. 3. A compound formedby reacting an aqueous phase, an organic phase and an additive, whereinthe aqueous phase comprises an amine, the organic phase comprises apolyacyl halide and the additive is a compound of the formula:

wherein R1 and R2 may be the same or different, and are C1-C20 alkyl oralkoxy groups; R3 may be a C1-C4 alkyl group, or H; Q is either —(CH₂)³—or —CH₂CH(CH₃)CH₂—; X is either —CH₂CH(OH)CH₂OH or H; a, b, c, d, e areintegers such that the sum of a+b+c+d+e is less than 100, if b is 0,then d or e must be greater than 0, if d is 0, then b or e must begreater than 0; and if e is 0, then b or d must be greater than 0; and,y1, y2, z1, z2 are each integers between 0 to
 10. 4. A compound formedby reacting an organic phase and an additive, wherein the organic phasecomprises a polyacyl halide and the additive is a compound of theformula:

wherein R is CH₃ to C₁₅H₃₁; X is 75% of —CH₂CH(OH)CH₂OH and 25% H; and nis an integer between 1 and
 100. 5. A compound formed by reacting anorganic phase and an additive, wherein the organic phase comprises apolyacyl halide and the additive is a compound of the formula:

wherein x is either —CH₂CH(OH)CH₂OH or H; and n is an integer between 4and
 100. 6. A compound formed by reacting an organic phase and anadditive, wherein the organic phase comprises a polyacyl halide and theadditive is a compound selected from the group consisting of:

wherein a and b are integers between 1 and 100 and the sum of a+b is notgreater than 100;

wherein a, b and c are integers between 1 and 100, the sum of a+b+c isnot greater than 100 and x is an integer between 1 and 50;


7. The compound of claim 2, wherein the polyacyl halide is trimesoylchloride.